ABSTRACT
The large bulk bandgap (1.35 eV) and Bohr radius (~10 nm) of InP semiconductor nanocrystals provides bandgap tunability over a wide spectral range, providing superior color tuning compared to that of CdSe quantum dots. In this paper, the dependence of the bandgap, photoluminescence emission, and exciton radiative lifetime of core/shell quantum dot heterostructures has been investigated using colloidal InP core nanocrystals with multiple diameters (1.5, 2.5, and 3.7 nm). The shell thickness and composition dependence of the bandgap for type-I and type-II heterostructures was observed by coating the InP core with ZnS, ZnSe, CdS, or CdSe through one to ten iterations of a successive ion layer adsorption and reaction (SILAR)-based shell deposition. The empirical results are compared to bandgap energy predictions made with effective mass modeling. Photoluminescence emission colors have been successfully tuned throughout the visible and into the near infrared (NIR) wavelength ranges for type-I and type-II heterostructures, respectively. Based on sizing data from transmission electron microscopy (TEM), it is observed that at the same particle diameter, average radiative lifetimes can differ as much as 20-fold across different shell compositions due to the relative positions of valence and conduction bands. In this direct comparison of InP/ZnS, InP/ZnSe, InP/CdS, and InP/CdSe core/shell heterostructures, we clearly delineate the impact of core size, shell composition, and shell thickness on the resulting optical properties. Specifically, Zn-based shells yield type-I structures that are color tuned through core size, while the Cd-based shells yield type-II particles that emit in the NIR regardless of the starting core size if several layers of CdS(e) have been successfully deposited. Particles with thicker CdS(e) shells exhibit longer photoluminescence lifetimes, while little shell-thickness dependence is observed for the Zn-based shells. Taken together, these InP-based heterostructures demonstrate the extent to which we are able to precisely tailor the material properties of core/shell particles using core/shell dimensions and composition as variables.
ABSTRACT
Heterostructured core/shell quantum dots (QDs) are prized in biomedical imaging and biosensing applications because of their bright, photostable emission and effectiveness as Förster resonance energy transfer (FRET) donors. However, as nanomaterials chemistry has progressed beyond traditional QDs to incorporate new compositions, ultra-thick shells, and alloyed structures, few of these materials have had their optical properties systematically characterized for effective application. For example, thick-shelled QDs, also known as 'giant' QDs (gQDs) are useful in single-particle tracking microscopy because of their reduced blinking, but we know only that CdSe/CdS gQDs are qualitatively brighter than thin-shelled CdSe/CdS in aqueous media. In this study, we quantify the impact of shell thickness on the nanoparticle molar extinction coefficient, quantum yield, brightness, and effectiveness as a FRET donor for CdSe/xCdS core/shell and CdSe/xCdS/ZnS core/shell/shell QDs, with variable thicknesses of the CdS shell (x). Molar extinction coefficients up to three orders of magnitude higher than conventional dyes and forty-fold greater than traditional QDs are reported. When thick CdS shells are combined with ZnS capping, quantum yields following thiol ligand exchange reach nearly 40%-5-10× higher than either the commercially available QDs or gQDs without ZnS caps treated the same way. These results clearly show that thick CdS shells and ZnS capping shells work in concert to provide the brightest possible CdSe-based QDs for bioimaging applications. We demonstrate that thicker shelled gQDs are over 50-fold brighter than their thin-shelled counterparts because of significant increases in their absorption cross-sections and higher quantum yield in aqueous milieu. Consistent with the point-dipole approximation commonly used for QD-FRET, these data show that thick shells contribute to the donor-acceptor distance, reducing FRET efficiency. Despite the reduction in FRET efficiency, even the thickest-shell gQDs exhibited energy transfer. Through this systematic study, we elucidate the tradeoffs between signal output, which is much higher for the gQDs, and FRET efficiency, which decreases with shell thickness. This study serves as a guide to nanobiotechnologists striving to use gQDs in imaging and sensing devices.
